Hydroaryl amino anthraquinone compounds and process of making the same



Patented Sept. 1, 1931 umran srAr s PATENT OFFICE 'KIAAUSiWLEINAND,-,OF ZEIAIT TARD, NEAR.COLOGNE-ON-THE-RHINE,GERMANY, ASSIGNOR TO GENERAL 'ANILINE 'WQRK'S, INCL, OF NEW YORK, N. 'Y., A CORPORATION OF iDEL WARE rrxnaoerwrnmmo AN HRAeUI oNE.coMPoUNDs AND PROCESS or MAKING THE a SAME invention relates-to amino-anthraquinone comp'ounds in which the aminogroups are l substituted by hydro-aromatic radicles. -Arylaminmanthraquinone compounds are *5 of tremendous importancein the dyestutl industry, some of the fastest and most brilliant wool colors beingsulfonated arylamino-anthraquinones. I have shown in U. S. Patent N 0. 1,735,147 is dated November .12, 1929 (application Ser. No. 130,112,1iled AugustlS, 1926) that by replacing the aryl-substituent in homonuclearal amino -4 7 arylamino-anthraquinone sulfonic acids,that means lamino--arylamino-anthraguinone-2-or. 3 sulfonic acids, by an aliphatic open carbon chain, or .alkyl radicle .the shade of .the original blue dyestuff is considerably improved, becoming I much brighter and clearer. The superior light fastness of wool dyeingsmade with 1 aminoA-arylaminoeanthraquinone sulfonic acids is however decreased, in the case'of the corresponding L alkyl. substituted dyestufi'. fzl jhave now found that when lhydro-aryl- 125; aminesare allowed to react in presence ofa copper catalyst upon .l aminoehalogeno-2- anthraquinone. .sul'fonic acids, 1-amino-4-hydriosaryl-amino+2-anthraquinone. sul fonic acids are obtained. These novel dyestuffs 1% dye animal fibresblue shades which show the superiorllight fastness of the corresponding'iarylcompounds as Well .asthe brightness and clearness of theidyeingsmade with the I allrylvcompounds. M a p 353 Ihave further found that, quite, generally, hydro-arylamino-anthraquinone compounds are distinguished from the corresponding arylycompojunds :by @very marked features, ,such as greater clearness and brightness of the shade of the dyestuif made out of them, while the novel products still possess the same valuable fastness to light. Such hydro-arylamino-anthraquinone compounds 4555 have therefore proven to be exceedingly valuable in the production of novel dyestufi's. I

The term hydro-aryl as used herein is meant to cover the products obtained by hydrogenating compounds of the benzene and KT; No Drawing. Application filed August 18, 1926, Serial No. 130,111, and in Germany November 23, 1925.

naphthalene series, as well as their derivatives such as hydroxy compounds, ethers and esters etc.

My novel hydro-arylamino-anthraquinone compounds can be produced by substantially the same reactions which lead to arylaminoanthraquinones, such as condensation of hydroxyor halogeno- ,anthraquinones with hydroarylalnines. It is however remarkable that the hydroarylamines, which are usually much more basic than the corresponding arylamines, react substantially only with the halogen atom when allowed to react in-presence of a copper catalystupon halogeno-anthraquinone sulfonic acids, such as l-amino-4-halogenoe2-sulfonic acid, and that the sulfo groupsare not attacked under the conditions whereas the halogen atoms are practically completely replaced by a hydroaryl-amino-residue.

Hydro arylaminoanthraquinone compounds containing sulfo groups in the nucleus can be Used directly as dyestuffs. Unsulfonate'd hydroa-rylamino-anthraquinones are preferably made soluble for use in the dyeing of animal fibres. Hydroxy-hydroarylamino-anthraquinones react with sulfuric acid to form sulfo esters which are easily Water soluble. Hydro arylamino-anthraquinones containing an aryl amino group can be easily sulfonated, the sulfo group entering most probably into'the aryl residue; in this manner water soluble dyestufi's are also produced.

The following examples will further illustrate my invention, the parts beingby weight.

Example 1.-2O parts l-amino bbromos2- I anthraquinone sulfonic acid, parts hexahydroaniline, 12parts-soda ash, 1 part copper sulfate are dissolved in 100 parts alcohol and 900 parts water and heated for two hours to boiling temperature. The solution turns blue. The excess hexahydroaniline and the alcohol are steamed oft and the residue salted out. The 1-amino--hexahydroanilino-2-anthraquinone sulfonic acid separates and is obtained as Water-solubleblue crystals. It dyes WOOl clear, intense blue shades of excellent fastness to light. It has most probably the formula:

- O COb SOaH \OO I omcm V NH-GH 011,

. om o11 E 03617702736 2.2O parts 1-amino-4-bromo-2- anthraquinone sulfonic acid, 60 parts hexahydro-o-toluidine, 10 parts soda ash, 1 part copper sulfate, 100 parts pyridine and 900 parts water are heated for 23 hours to boiling temperature. 7 The dyestufi forms quickly and is isolated as described in Example 1. The 1 amino 4- hexahydro -otoluido -2lanthraquinone sulfonic acid is obtained as greenish-blue water soluble crystals, and dyes wool 'very clear greenish-blue shades, fast to Example 3.10 parts leuco-l-l-dihydroxy anthraquinone are dissolved at about 100 C- inlOO parts o-amino-cyclo-hexanol and kept at this temperature for about one hour, the reaction mass is then diluted with 100 parts alcohol, crystals separate and are filtered 05. They represent the ll di-o-hydroxy-cyclohexylamino-anthraquinone of the most probable formula: V

. V on '/(|3H-CH2 NH-CH 011;

The hydroxyl groups in the hydroaryl residue are e-sterified when the above compound is treated with sulfuric acid. The so obtained sulfuric acid ester of the 1- 4 -di-o-hydroxy cyclohexylamino anthraquinone is easily soluble in water and dyes wool particularly clear blue shades of good fastness to light.

Emample 4.10 parts hexahydroaniline, parts pyridine, 50 parts water and 10 parts 1-methoXy-4l-toluido-anthraquinone are heated for about two hours under pressure to a temperature of 125 C. The l-hexahydroanilino-t-toluido-anthraquinone formed is filtered off after cooling. It'is a blue crystalline powder and has most probably the formula:

. OHz-OHz NHGH V OH2 0HzOHz i O C O n i I NH By treatment with sulfuric acid a sulfonic acid is obtained which dyes wool exceedingly clear, greenish-blue shades of good light fastness.

I claim:

1. As new products amino-anthraquinone compounds, the distinctive characteristic of which is that one of the amine hydrogens is:

substituted by a hydroaryl radicle.

' 2. As new products l-aminol-hydroaryl amino-Q-anthraquinone sulfonic acids, which are water soluble, blue, crystalline substances,

dyeing wool exceedingly clear, blue shades,

fast to light.

3. As a new product the l-aminol-hexahydroanilino-Z-anthraquinone sulfonic acid, which crystallizes in blue needles, is soluble in water with a blue color, dyes wool exceedingly clear, blue shades fast to light and has most probably the formula:

NH: O o o s03 1 1 \co/ /GH2OH2 NE-OH OH2 OHrCHa 4:. The process of reacting in presence of a copper catalyst with hydroarylamines upon 1 amino 4: halogeno 2 anthraquinone V sulfonic acids. 1 I

5. The process of reacting in presence of a copper catalyst with hydroarylamines upon l-amino- -halogeno 2 anthraquinone sulfonic acids, in which the halogen is-one of the group comprising chlorine and bromine.

6. The process of reacting in presence of a copper catalyst with a hydroarylamine upon KLAUS WEINAND.

sulfonic 

